Additive impregnated composition useful in the catalytic hydroprocessing of hydrocarbons, a method of making such catalyst, and a process of using such catalyst

ABSTRACT

A composition that comprises a support material that is loaded with an active metal or metal precursor and an additive that comprises an ether amine compound and, preferably, a morpholine compound as an additional component of the ether amine containing additive. The ether amine containing additive impregnated composition is useful in the hydroprocessing of hydrocarbon feedstocks. The ether amine containing additive impregnated composition is prepared by incorporating a metal solution into a support material followed by incorporating therein the ether amine containing additive.

This application claims the benefit of U.S. Provisional Application No.61/501,877 filed Jun. 28, 2011, the entire disclosure of which is herebyincorporated by reference.

This invention relates to a composition that is impregnated with anadditive that is useful in the catalytic hydroprocessing ofhydrocarbons, a method of making such a composition, and its use in thecatalytic hydroprocessing of hydrocarbon feedstocks.

Hydroprocessing catalysts are used in the removal of organic sulfur andnitrogen compounds from hydrocarbon feedstocks that are typicallyderived from the distillation of crude petroleum. The organic sulfur andnitrogen compounds are catalytically converted in the presence ofhydrogen respectively to hydrogen sulfide and ammonia to thensubsequently be removed from the hydrotreated feedstock. Generally, suchhydroprocessing catalysts include a carrier having deposited thereon aGroup VIB metal, such as molybdenum and tungsten, and a Group VIIImetal, such as nickel and cobalt. Phosphorus may also be present in thehydroprocessing catalyst. One method of preparing a hydroprocessingcatalyst includes the impregnation of a carrier with the hydrogenationmetal components followed by calcination of the impregnated carrier toconvert the metal components into oxides. The calcined catalyst is thensubjected to a sulfidation treatment to convert the metal oxides tometal sulfide.

U.S. Pat. No. 6,329,314 discloses a process for the activation of ahydroconversion catalyst that contains a Group VIII metal component and,optionally, a Group VI metal component by impregnating the catalyst witha liquid phase petroleum fraction, a thionic compound and a nitrogenouscompound under certain specified conditions.

U.S. Pat. No. 6,540,908 discloses a process for preparing a sulfidedhydrotreating catalyst. This process involves combining a catalystcarrier of alumina and a hydrogenation metal catalyst carrier with anorganic compound that includes a covalently bonded nitrogen atom and acarbonyl moiety followed by sulfiding the resulting combination.

U.S. Pat. No. 7,235,173 discloses a hydrotreating catalyst that containsat least one group VIB and/or group VIII metal and, optionally,phosphorus and/or silicon with an organic compound additive. It isessential that the organic additive have at least one nitrogen atom.Examples of compounds that correspond to the generic general formularepresentative of possible organic additives of the hydrotreatingcatalyst include those selected from the group consisting ofhexamethylene diamine, monoethanolamine, diethanolamine,triethanolamine, N,N-dimethyl-N′-ethylethylene diamine, amino alcoholand amino alkoxysilane. The organic additive can be introduced onto thehydrotreatment catalyst by dry impregnation, or by co-impregnationsimultaneously with the metals, or by deposition during sulfurization ofthe catalyst.

US 2009/0038993 discloses a hydrocarbon oil-impregnated composition thatcomprises a support material having incorporated therein a metalcomponent and impregnated with a hydrocarbon oil. The hydrocarbonoil-impregnated composition is useful in hydrotreating of hydrocarbonfeedstocks. In the preparation of the hydrocarbon oil-impregnatedcomposition a support material that is loaded with a metal precursor isuncalcined and non-sulfided when it is impregnated with the hydrocarbonoil. The hydrocarbon oil-impregnated composition exhibits betterhydrodesulfurization catalytic activity than does certain non-oilimpregnated compositions and it exhibits good catalytic stability.

US 2010/0236988 discloses a hydroprocessing catalyst composition thatcomprises a support material having incorporated therein a metalcomponent and impregnated with both a hydrocarbon oil and a polaradditive. The oil and polar additive impregnated composition is preparedby incorporating into a calcined support material that is loaded with anactive metal precursor, but not subsequently calcined or sulfide, thehydrocarbon oil and polar additive. The oil and polar additiveimpregnated composition exhibits good hydrodesulfurization catalyticactivity.

There is an ongoing need to find improved higher activity hydrotreatingcatalysts and, thus, it is one objective of this invention to provide acomposition that is useful and highly active in the catalytichydrotreating of hydrocarbon feedstocks and a method of preparing such acomposition.

Accordingly, provided is a composition that comprises a support materialthat is loaded with an active metal precursor and an additive comprisingat least 20 vol. % of an ether amine compound. The composition may bemade by incorporating a metal-containing solution into a supportmaterial to provide a metal-incorporated support material; andincorporating an additive comprising at least 20 vol. % of an etheramine compound into said metal-incorporated support material to therebyprovide an additive impregnated composition comprising at least 20 vol.% of an ether amine compound. The inventive composition may further beused by contacting a hydrocarbon feedstock under hydrotreating processconditions with the inventive composition.

Published patent application US 2010/0236988, which is herebyincorporated herein by reference, discloses an inventive compositionthat utilizes a polar additive, such as dimethylformamide (DMF), incombination with a hydrocarbon oil to provide a composition that isespecially useful in applications involving the catalytichydroprocessing of hydrocarbon feedstocks. While these inventivecompositions have been found to have very beneficial properties, the useand application of certain of the polar additives with hydrocarbon oilcan be difficult. Certain of the more desirable polar additives can havephysical properties that make them hard to handle. For instance, some ofthe polar additives can have a low flash point. Due to their volatility,the handling of these low flash point additives often will requirespecial procedures.

It is also noted in US 2010/0236988 that due to the physicalcharacteristics of certain hydrocarbon oils and polar additives,typically, an emulsion of the two components with one of the componentsbeing dispersed in the other is formed to provide a mixture or blend ofthe two components for impregnation of a metal loaded support material.Because of this lack of miscibility of the polar additive withhydrocarbon oil, the two components generally are required to beseparately stored and special blending equipment is needed to form anemulsion of the components immediately prior to the incorporation of theblend into the support material of the composition.

It is further thought that even after the incorporation of thehydrocarbon oil and polar additive blend into the support material ofthe composition the additive components may even undergo a separationinto two separate phases. While it is not know with any certainty, it ispossible that this phase separation may have an impact on theperformance of the final catalyst.

The composition of the invention is one which is particularly useful inthe catalytic hydroprocessing of petroleum derived or other hydrocarbonfeedstocks, or the composition of the invention is one which isconvertible by the treatment with hydrogen or a sulfur compound, orboth, into a catalyst composition having particularly good catalyticproperties in the hydroprocessing of hydrocarbon feedstocks.

It has been discovered that by using an ether amine compound as anadditive with a support material or carrier that is loaded with acatalytically active metal compound or metal precursor the activity ofthe composition when used in the hydrodesulfurization (HDS) orhydrodenitrogenation (HDN) of hydrocarbon feedstocks can be enhanced. Itfurther has been discovered that the use of the ether amine compound incombination with another additive, such as a polar additive as describedin US 2010/0236988, or a solvent that includes in its molecularstructure both amine and ether functional groups, such as morpholine,and, in particular, n-formylmorpholine, provides for even a greaterenhancement in HDS or HDN catalytic activity than when the ether aminecompound is used alone.

The use of the ether amine compound as an additive of the inventivecomposition is particularly desirable due to its reasonably high flashpoint which makes it easier to handle, store and use than certain of theprior art additives, such as the polar additive, DMF. And, when theether amine compound is to be combined with a morpholine compound suchas, for example, n-formylmorpholine (NFM), due to the two compoundsbeing miscible, there is no need to use the special blending methodsrequired to form an emulsion as when certain hydrocarbon oils areblended with certain polar additives. A miscible mixture of the etheramine and morpholine compounds of the invention is more easily formedthan an emulsion, and the impregnation of the miscible mixture into asupport material or carrier that is loaded with or comprises an activemetal component or active metal precursor is much easier to perform.

The composition of the invention includes a support material that hasincorporated therein or is loaded with a metal component, which is orcan be converted to a metal compound that has activity towards thecatalytic hydrogenation of organic sulfur and nitrogen compounds, or,otherwise, the metal component is useful in the hydrodesulfurization(HDS) or hydrodenitrogenation (HDN) of hydrocarbon feedstocks. Thissupport material which contains the metal component further hasincorporated therein an additive that comprises at least a suitableether amine compound, and, preferably, a combination of such ether aminecompound and a morpholine compound, to thereby provide an additiveimpregnated composition of the invention.

The support material of the inventive composition can comprise anysuitable inorganic oxide material that is typically used to carrycatalytically active metal components. Examples of possible usefulinorganic oxide materials include alumina, silica, silica-alumina,magnesia, zirconia, boria, titania and mixtures of any two or more ofsuch inorganic oxides. The preferred inorganic oxides for use in theformation of the support material are alumina, silica, silica-aluminaand mixtures thereof. Most preferred, however, is alumina.

In the preparation of various embodiments of the inventive composition,the metal component of the composition may be incorporated into thesupport material by any suitable method or means that provides thesupport material that is loaded with an active metal precursor. Thus,the composition includes or comprises the support material and a metalcomponent.

One method of incorporating the metal component into the supportmaterial, includes, for example, co-mulling the support material withthe active metal or metal precursor to yield a co-mulled mixture of thetwo components. Or, another method includes the co-precipitation of thesupport material and metal component to form a co-precipitated mixtureof the support material and metal component. Or, in a preferred method,the support material is impregnated with the metal component using anyof the known impregnation methods, such as incipient wetness, toincorporate the metal component into the support material.

When using the impregnation method to incorporate the metal componentinto the support material, it is preferred for the support material tobe formed into a shaped particle comprising an inorganic oxide materialand thereafter loading the shaped particle with an active metalprecursor, preferably, by the impregnation of the shaped particle withan aqueous solution of a metal salt to give the support materialcontaining a metal of a metal salt solution.

To form the shaped particle, the inorganic oxide material, whichpreferably is in powder form, is mixed with water and, if desired orneeded, a peptizing agent and/or a binder to form a mixture that can beshaped into an agglomerate. It is desirable for the mixture to be in theform of an extrudable paste suitable for extrusion into extrudateparticles, which may be of various shapes such as cylinders, trilobes,etc. and nominal sizes such as 1/16″, ⅛″, 3/16″, etc. The supportmaterial of the inventive composition, thus, preferably, is a shapedparticle comprising an inorganic oxide material.

The shaped particle is then dried under standard drying conditions thatcan include a drying temperature in the range of from 50° C. to 200° C.,preferably, from 75° C. to 175° C., and, most preferably, from 90° C. to150° C. After drying, the shaped particle is calcined under standardcalcination conditions that can include a calcination temperature in therange of from 250° C. to 900° C., preferably, from 300° C. to 800° C.,and, most preferably, from 350° C. to 600° C.

The calcined shaped particle can have a surface area (determined by theBET method employing N₂, ASTM test method D 3037) that is in the rangeof from 50 m²/g to 450 m²/g, preferably from 75 m²/g to 400 m²/g, and,most preferably, from 100 m²/g to 350 m²/g. The mean pore diameter inangstroms (Å) of the calcined shaped particle is in the range of from 50to 200, preferably, from 70 to 150, and, most preferably, from 75 to125. The pore volume of the calcined shaped particle is in the range offrom 0.5 cc/g to 1.1 cc/g, preferably, from 0.6 cc/g to 1.0 cc/g, and,most preferably, from 0.7 to 0.9 cc/g. Less than ten percent (10%) ofthe total pore volume of the calcined shaped particle is contained inthe pores having a pore diameter greater than 350 Å, preferably, lessthan 7.5% of the total pore volume of the calcined shaped particle iscontained in the pores having a pore diameter greater than 350 Å, and,most preferably, less than 5%.

The references herein to the pore size distribution and pore volume ofthe calcined shaped particle are to those properties as determined bymercury intrusion porosimetry, ASTM test method D 4284. The measurementof the pore size distribution of the calcined shaped particle is by anysuitable measurement instrument using a contact angle of 140° with amercury surface tension of 474 dyne/cm at 25° C.

In a preferred embodiment of the invention, the calcined shaped particleis impregnated with a metal component by use of one or more impregnationsteps using one or more aqueous solutions containing at least one metalsalt wherein the metal compound of the metal salt solution is an activemetal or active metal precursor. The metal elements are those selectedfrom Group 6 of the IUPAC Periodic Table of the elements (e.g., chromium(Cr), molybdenum (Mo), and tungsten (W)) and Groups 9 and 10 of theIUPAC Periodic Table of the Elements (e.g., cobalt (Co) and nickel(Ni)). Phosphorous (P) is also a desired metal component. For the Group9 and 10 metals, the metal salts include Group 9 or 10 metal acetates,formats, citrates, oxides, hydroxides, carbonates, nitrates, sulfates,and two or more thereof. The preferred metal salts are metal nitrates,for example, such as nitrates of nickel or cobalt, or both. For theGroup 6 metals, the metal salts include Group 6 metal oxides orsulfides. Preferred are salts containing the Group 6 metal and ammoniumion, such as ammonium heptamolybdate and ammonium dimolybdate.

The concentration of the metal compounds in the impregnation solution isselected so as to provide the desired metal content in the finalcomposition of the invention taking into consideration the pore volumeof the support material into which the aqueous solution is to beimpregnated and the amount of additive that is to be later incorporatedinto the support material that is loaded with a metal component.Typically, the concentration of metal compound in the impregnationsolution is in the range of from 0.01 to 100 moles per liter.

The metal content of the support material having a metal componentincorporated therein may depend upon the application for which theadditive impregnated composition of the invention is to be used, but,generally, for hydroprocessing applications, the Group 9 and 10 metalcomponent, i.e., cobalt or nickel, preferably, nickel, can be present inthe support material having a metal component incorporated therein in anamount in the range of from 0.5 wt. % to 20 wt. %, preferably from 1 wt.% to 15 wt. %, and, most preferably, from 2 wt. % to 12 wt. %. The Group6 metal component, i.e., molybdenum or tungsten, preferably, molybdenum,can be present in the support material having a metal componentincorporated therein in an amount in the range of from 5 wt. % to 50 wt.%, preferably from 8 wt. % to 40 wt. %, and, most preferably, from 12wt. % to 30 wt. %. The above-referenced weight percents for the metalcomponents are based on the dry support material and the metal componentas the element regardless of the actual form of the metal component.

To provide the additive impregnated composition of the invention, asuitable ether amine containing additive is incorporated into thesupport material that also has incorporated therein, as described above,the metal component or active metal precursor. The ether aminecontaining additive is used to fill a significant portion of theavailable pore volume of the pores of the support material, which isalready loaded with the active metal precursor, to thereby provide acomposition that comprises a support material containing a metalcomponent and an additive comprising an ether amine compound.

The additive impregnated composition may be installed, as is, into areactor vessel or within a reactor system that is to undergo a start-upprocedure in preparation of or prior to the introduction of a sulfidingfeed that can include a sulfiding agent or a hydrocarbon feedstockcontaining a concentration of an organic sulfur compound.

It is a significant aspect of the invention that the support materialloaded with an active metal precursor is not calcined or sulfided priorto its loading into a reactor vessel or system for its ultimate use as ahydrodesulfurization or hydrodenitrogenation catalyst. It can, however,be sulfided, in situ, in a delayed feed introduction start-up procedure.The delayed feed introduction start-up procedure is hereinafter morefully described.

In the preparation of the inventive composition, any suitable method ormeans may be used to impregnate the metal loaded support material withthe ether amine containing additive. When the additive comprises morethan one component such as an ether amine compound andn-formylmorpholine, the impregnation with the additive combination maybe done by separately impregnating the metals loaded support materialwith the ether amine compound and with the n-formylmorpholine, orcoincidentally impregnating the metals loaded support material with anadditive mixture of the ether amine compound and n-formylmorpholine.

It is preferred to impregnate the metal loaded support material with amixture or blend of the ether amine compound and n-formylmorpholine. Theether amine compound and n-formylmorpholine should be present in themixture or blend thereof in the desired relative amounts. One of thespecific benefits of using the ether amine compound andn-formylmorpholine is that they a miscible and so the formation of anemulsion is not required. Blending of the two components is easier thanthe blending of certain alternative additive mixtures, and theimpregnation of the metal loaded support material with the miscibleblend of ether amine compound and n-formylmorpholine is also easier toconduct.

The preferred method of impregnation may be any standard well-known porefill methodology whereby the pore volume is filled by taking advantageof capillary action to draw the liquid into the pores of the metalloaded support material. It is desirable to fill at least 75% of thepore volume of the metal loaded support material with the ether aminecontaining additive. It is preferred for at least 80% of the pore volumeof the metal loaded support material to be filled with the ether aminecontaining additive, and, most preferred, at least 90% of the porevolume is filled with the ether amine containing additive.

While the use of an ether amine compound alone as an additive in themetal loaded support material provides a composition exhibitingparticularly good HDS and HDN activities, it further has been found thatthe use of the ether amine compound in combination withn-formylmorpholine in the metal loaded support material provides an evengreater catalytic benefit than with the use of the ether amine compoundalone. Thus, the relative weight ratio of n-formylmorpholine to etheramine compound incorporated into the metal loaded support material canbe important. When the additive that is incorporated into the metalloaded support material is a combination or mixture of an ether aminecompound and n-formylmorpholine, the relative weight ratio ofn-formylmorpholine to ether amine compound should be in the rangeupwardly to 10:1 (10 weight parts n-formylmorpholine to 1 weight partether amine compound), for example, the weight ratio may be in the rangeof from 0:1 to 10:1. For a binary mixture of n-formylmorpholine andether amine compound, this is in the range of from 0 wt % to 91 wt %n-formylmorpholine, based on the weight of the binary mixture.

Typically, the relative weight ratio of n-formylmorpholine to etheramine compound incorporated into the metal loaded support materialshould be in the range of from 0.01:1 (1 wt % for binary mixture) to 9:1(90 wt % for a binary mixture). Preferably, this relative weight ratiois in the range of from 0.1:1 (9 wt % for binary mixture) to 8:1 (89 wt% for a binary mixture), more preferably, from 0.2:1 (17 wt % for abinary mixture) to 7:1 (87 wt % for a binary mixture), and, mostpreferably, it is in the range of from 0.25:1 (20 wt % for a binarymixture) to 6:1 (86 wt % for a binary mixture).

A typical commercial blend of a mixture, comprising n-formylmorpholineand ether amine compound, that is used to impregnate the metal-loadedsupport material contains n-formylmorpholine in the range of from 10 wt% to 90 wt % of the total weight of the mixture, and the ether aminecompound in the range of from 10 wt % to 90 wt % of the total weight ofthe mixture. It is desirable, however, for the n-formylmorpholine to bepresent in the mixture at a concentration in the range of from 15 wt %to 60 wt % with the ether amine compound being present in the mixture ata concentration in the range of from 40 wt % to 85 wt %. Preferably, then-formylmorpholine is present in the mixture at a concentration in therange of from 20 wt % to 40 wt % with the ether amine compound beingpresent in the mixture at a concentration in the range of from 60 wt %to 80 wt %.

Any suitable ether amine compound may be used as the additive orcomponent of the ether amine containing additive of the invention aslong it has the required physical properties and provides for thedesired catalytic properties of the invention. An important property ofthe ether amine compound is for it to be substantially soluble ormiscible with n-formylmorpholine at the temperature of 25° C. (77° F.).

Another of the important physical properties of the ether amine compoundof the invention is for it to have a reasonably high flash point thatmakes its handling easier and less problematic than with the handling ofcertain low flash point prior art additives. It is desirable for theflash point of the ether amine compound of the additive to be at least80° C. (176° F.), preferably, the flash point of the ether aminecompound is at least 85° C. (185° F.), and, more preferably, the flashpoint is at least 90° C. (194° F.). The ether amine compound also shouldat least be in the liquid state at a temperature of about 5° C. (41° F.)or higher, or at 10° C. (50° F.) or higher, or at 15° C. (59° F.).

The ether amine compound also will have a molecular weight in the rangeof from about 165 to about 300. More typically, the molecular weight ofthe ether amine compound is in the range of from 185 to 280, and, mosttypically, the molecular weight is in the range of from 200 to 265.

Potential ether amine compounds suitable for use as the additive or acomponent of the ether amine containing additive may be compoundsselected from the family of compounds having the following formula:R—O—(CH₂)_(n)NH₂, wherein R is an alkyl functional group comprising from4 to 14 carbon atoms and n is an integer ranging from 1 to 6. Specificexamples of possible suitable ether amine compounds include thoseselected from the group of ether amine compounds consisting ofhexyloxypropyl amine, isohexyloxypropyl amine, 2-ethylhexyloxypropylamine, octyloxypropylamine, decycloxypropyl amine, isodecyloxypropylamine, dodecyloxypropylamine, isododecyloxypropyl amine,isotridecyloxypropyl amine, and mixtures of any two or more thereof. Twoparticularly useful ether amine compounds include octyloxypropyl amineand decyloxypropyl amine and mixtures thereof.

The ether amine containing additive that is incorporated into themetal-incorporated support material should have a sufficient amount ofthe ether amine compound so as to provide the catalytic benefits asdescribed herein. Generally, the additive is to comprise at least 20 vol% of the ether amine compound up to essentially 100 vol % of theadditive. The ether amine containing additive may also include othercomponents such as an inert solvent or other substantially inertcompound that is mixable with the ether amine compound. When the etheramine compound is used alone, that is, without combining it with themorpholine compound, it is preferred for the additive to comprise atleast 50 vol % of the ether amine compound. It is more preferred in thiscase for the additive to comprise at least 80 vol %, and it is mostpreferred for the additive to comprise at least 90 vol % and even atleast 95 vol %.

When the additive that is incorporated into the support material loadedwith an active metal component or metal precursor includes both theether amine compound and the morpholine compound, which is preferablyn-formylmorpholine, the relative ratios of each component present in theadditive are as described herein. In this case, the additive may be, andpreferably is, a predominantly binary mixture of the ether aminecompound and morpholine with each component being present in the ratiosas described above. The additive, however, may include other componentssuch as an inert solvent or other substantially inert compound.

A particularly important aspect of the invention is for the supportmaterial having a metal component incorporated therein to be uncalcinedand non-sulfided when it is impregnated with the ether amine containingadditive. Cost savings in the preparation of the composition arerealized by not having to perform the calcination or sulfidation steps.

Before the incorporation of the ether amine containing additive into thesupport material having a metal component incorporated therein,particularly when the metal component is added to the support materialby impregnation using an aqueous solution of a metal salt(metal-impregnated support material), it is important for thismetal-impregnated support material to be dried so as to remove at leasta portion of the volatile liquid contained within the pores of thesupport material so as to provide pore volume that can be filled withthe ether amine containing additive. The metal-impregnated supportmaterial, thus, is dried under drying conditions that include a dryingtemperature that is less than a calcination temperature.

A significant feature of the invention is for the drying temperatureunder which the drying step is conducted to not exceed a calcinationtemperature. Thus, the drying temperature should not exceed 400° C.,and, preferably, the drying temperature at which the metal-impregnatedsupport material is dried does not exceed 300° C., and, most preferably,the drying temperature does not exceed 250° C. It is understood that thedrying step will, in general, be conducted at lower temperatures thanthe aforementioned temperatures, and, typically, the drying temperaturewill be conducted at a temperature in the range of from 60° C. to 150°C.

The drying of the metal-impregnated support material is preferablycontrolled in a manner so as to provide the resulting driedmetal-impregnated support material having a volatiles content that is ina particular range. The volatiles content of the dried metal-impregnatedsupport material should be controlled so that it does not exceed 20 wt.% LOI.

The LOI, or loss on ignition, is defined as the percentage weight lossof the material after its exposure to air at a temperature of 482° C.for a period of two hours, which can be represented by the followingformula: (sample weight before exposure less sample weight afterexposure) multiplied by 100 and divided by (sample weight beforeexposure). It is preferred for the LOI of the dried metal-impregnatedsupport material to be in the range of from 1 wt. % to 20 wt. %, and,most preferred, from 3 wt. % to 15 wt. %. The dried metal-impregnatedsupport material is further impregnated with the additive as describedherein.

The ether amine containing additive impregnated composition of theinvention may be treated, either ex situ or in situ, with hydrogen andwith a sulfur compound, and, indeed, it is one of the beneficialfeatures of the invention that it permits the shipping and delivery of anon-sulfurized composition to a reactor in which it can be activated, insitu, by a hydrogen treatment step followed by a sulfurization step. Asearlier noted, the ether amine containing additive impregnatedcomposition can first undergo a hydrogen treatment that is then followedwith treatment with a sulfur compound.

The hydrogen treatment includes exposing the ether amine containingadditive impregnated composition to a gaseous atmosphere containinghydrogen at a temperature ranging upwardly to 250° C. Preferably, theether amine containing additive impregnated composition is exposed tothe hydrogen gas at a hydrogen treatment temperature in the range offrom 100° C. to 225° C., and, most preferably, the hydrogen treatmenttemperature is in the range of from 125° C. to 200° C.

The partial pressure of the hydrogen of the gaseous atmosphere used inthe hydrogen treatment step generally can be in the range of from 1 barto 70 bar, preferably, from 1.5 bar to 55 bar, and, most preferably,from 2 bar to 35 bar. The ether amine containing additive impregnatedcomposition is contacted with the gaseous atmosphere at theaforementioned temperature and pressure conditions for a hydrogentreatment time period in the range of from 0.1 hours to 100 hours, and,preferably, the hydrogen treatment time period is from 1 hour to 50hours, and most preferably, from 2 hours to 30 hours.

Sulfiding of the ether amine containing additive impregnated compositionafter it has been treated with hydrogen can be done using anyconventional method known to those skilled in the art. Thus, thehydrogen treated ether amine containing additive impregnated compositioncan be contacted with a sulfur-containing compound, which can behydrogen sulfide or a compound that is decomposable into hydrogensulfide, under the contacting conditions of the invention. Examples ofsuch decomposable compounds include mercaptans, CS₂, thiophenes,dimethyl sulfide (DMS), and dimethyl disulfide (DMDS). Also, preferably,the sulfiding is accomplished by contacting the hydrogen treatedcomposition, under suitable sulfurization treatment conditions, with ahydrocarbon feedstock that contains a concentration of a sulfurcompound. The sulfur compound of the hydrocarbon feedstock can be anorganic sulfur compound, particularly, one which is typically containedin petroleum distillates that are processed by hydrodesulfurizationmethods.

Suitable sulfurization treatment conditions are those which provide forthe conversion of the active metal components of the hydrogen treatedether amine containing additive impregnated composition to theirsulfided form. Typically, the sulfiding temperature at which thehydrogen treated ether amine containing additive impregnated compositionis contacted with the sulfur compound is in the range of from 150° C. to450° C., preferably, from 175° C. to 425° C., and, most preferably, from200° C. to 400° C.

When using a hydrocarbon feedstock that is to be hydrotreated using thecatalyst composition of the invention to sulfide the hydrogen treatedcomposition, the sulfurization conditions can be the same as the processconditions under which the hydrotreating is performed. The sulfidingpressure at which the hydrogen treated ether amine containing additiveimpregnated composition is sulfided generally can be in the range offrom 1 bar to 70 bar, preferably, from 1.5 bar to 55 bar, and, mostpreferably, from 2 bar to 35 bar.

As noted above, one of the benefits provided by the ether aminecontaining additive impregnated composition of the invention is that itcan be utilized in a reactor system that is started up using a so-calleddelayed feed introduction procedure. In the delayed feed introductionprocedure, the reactor system, which includes a reactor vesselcontaining the ether amine containing additive impregnated composition,first undergoes a heating step to raise the temperature of the reactorand the ether amine containing additive impregnated compositioncontained therein in preparation for the introduction of a sulfidingagent or heated hydrocarbon feedstock for processing. This heating stepincludes introducing into the reactor the hydrogen-containing gas at theaforementioned hydrogen treatment conditions. After the hydrogentreatment of the ether amine containing additive impregnatedcomposition, it is thereafter treated with a sulfur compound in themanner as earlier described herein.

In hydrotreating applications, the impregnated composition, preferablyis used in a delayed feed introduction procedure or otherwise treatedwith hydrogen and sulfur, as described above. In this procedure, theimpregnated composition is contacted under suitable hydrodesulfurizationconditions with a hydrocarbon feedstock that typically has aconcentration of sulfur. This provides for sulfiding of the impregnatedcomposition.

One hydrocarbon feedstock that may be processed using the inventivecomposition is a petroleum middle distillate cut having a boilingtemperature at atmospheric pressure in the range of from 140° C. to 410°C. These temperatures are approximate initial and boiling temperaturesof the middle distillate. Examples of refinery streams intended to beincluded within the meaning of middle distillate include straight rundistillate fuels boiling in the referenced boiling range, such as,kerosene, jet fuel, light diesel oil, heating oil, heavy diesel oil, andthe cracked distillates, such as FCC cycle oil, coker gas oil, andhydrocracker distillates. The preferred distillate feedstock is a middledistillate boiling in the diesel boiling range of from about 140° C. to400° C.

The gas oils may also be processed using the inventive composition.These gas oils may include atmospheric gas oil, light vacuum gas oil,and heavy vacuum gas oil. It is further contemplated that the inventivecomposition may have use in the treatment of residuum feedstocks, aswell.

The sulfur concentration of the middle distillate feedstock can be ahigh concentration, for instance, being in the range upwardly to about 2weight percent of the distillate feedstock based on the weight ofelemental sulfur and the total weight of the distillate feedstockinclusive of the sulfur compounds. However, the distillate feedstocktypically has a sulfur concentration in the range of from 0.01 wt. %(100 ppmw) to 1.8 wt. % (18,000). But, more typically, the sulfurconcentration is in the range of from 0.1 wt. % (1000 ppmw) to 1.6 wt. %(16,000 ppmw), and, most typically, from 0.18 wt. % (1800 ppmw) to 1.1wt. % (11,000 ppmw). It is understood that the references herein to thesulfur content of the distillate feedstock are to those compounds thatare normally found in a distillate feedstock or in the hydrodesulfurizeddistillate product and are chemical compounds that contain a sulfur atomand which generally include organosulfur compounds.

The impregnated composition of the invention may be employed as a partof any suitable reactor system that provides for contacting it or itsderivatives with the distillate feedstock under suitablehydrodesulfurization conditions that may include the presence ofhydrogen and an elevated total pressure and temperature. Such suitablereaction systems can include fixed catalyst bed systems, ebullatingcatalyst bed systems, slurried catalyst systems, and fluidized catalystbed systems. The preferred reactor system is that which includes a fixedbed of the inventive catalyst contained within a reactor vessel equippedwith a reactor feed inlet means, such as a feed nozzle, for introducingthe distillate feedstock into the reactor vessel, and a reactor effluentoutlet means, such as an effluent outlet nozzle, for withdrawing thereactor effluent or the treated hydrocarbon product or the ultra-lowsulfur distillate product from the reactor vessel.

The hydroprocessing process generally operates at a hydroprocessingreaction pressure in the range of from 689.5 kPa (100 psig) to 13,789kPa (2000 psig), preferably from 1896 kPa (275 psig) to 10,342 kPa (1500psig), and, more preferably, from 2068.5 kPa (300 psig) to 8619 kPa(1250 psig).

The hydroprocessing reaction temperature is generally in the range offrom 200° C. (392° F.) to 420° C. (788° F.), preferably, from 260° C.(500° F.) to 400° C. (752° F.), and, most preferably, from 320° C. (608°F.) to 380° C. (716° F.).

It is recognized that one of the unexpected features from the use of theinventive composition is that it exhibits higher catalytic activity thancertain other alternative catalyst compositions, and, thus, it will, ingeneral, provide for comparatively lower required process temperaturesfor a given amount of desulfurization or denitrogenation, or both.

The flow rate at which the hydrocarbon feedstock is charged to thereaction zone of the inventive process is generally such as to provide aliquid hourly space velocity (LHSV) in the range of from 0.01 hr⁻¹ to 10hr⁻¹. The term “liquid hourly space velocity”, as used herein, means thenumerical ratio of the rate at which the hydrocarbon feedstock ischarged to the reaction zone of the inventive process in volume per hourdivided by the volume of catalyst contained in the reaction zone towhich the hydrocarbon feedstock is charged. The preferred LHSV is in therange of from 0.05 hr⁻¹ to 5 hr⁻¹, more preferably, from 0.1 hr⁻¹ to 3hr⁻¹ and, most preferably, from 0.2 hr⁻¹ to 2 hr⁻¹.

It is preferred to charge hydrogen along with the hydrocarbon feedstockto the reaction zone of the inventive process. In this instance, thehydrogen is sometimes referred to as hydrogen treat gas. The hydrogentreat gas rate is the amount of hydrogen relative to the amount ofhydrocarbon feedstock charged to the reaction zone and generally is inthe range upwardly to 1781 m³/m³ (10,000 SCF/bbl). It is preferred forthe treat gas rate to be in the range of from 89 m³/m³ (500 SCF/bbl) to1781 m³/m³ (10,000 SCF/bbl), more preferably, from 178 m³/m³ (1,000SCF/bbl) to 1602 m³/m³ (9,000 SCF/bbl), and, most preferably, from 356m³/m³ (2,000 SCF/bbl) to 1425 m³/m³ (8,000 SCF/bbl).

The hydrotreated product yielded from the process of the invention haslow or reduced sulfur and nitrogent concentrations relative to thehydrocarbon feedstock.

The following examples are presented to further illustrate certainaspects of the invention, but they are not to be construed as limitingthe scope of the invention.

EXAMPLE I

This Example I describes the preparation of a comparative compositionthat contains a prior art additive and of the inventive compositionsthat contain the additives of the invention.

A commercially available alumina carrier was used in the preparation ofthe catalyst compositions of this Example I. The following Table 1presents the typical physical properties of the alumina carrier that wasused in the preparations.

TABLE 1 Typical Alumina Carrier Properties Property Value Compacted BulkDensity(g/cc) 0.49 Water Pore Volume (cc/g) 0.88 BET Surface Area (m2/g)300 Median Pore Diameter by Volume (angstroms) 91

The metal components of the catalyst were incorporated into the carrierby the incipient wetness impregnation technique. The impregnationsolution included 75.6 weight parts water, 11.8 weight parts phosphoricacid (H₃PO₄), 12.8 weight parts nickel carbonate (NiCO₃), and 35.3weight parts Climax molybdenum trioxide (62.5% Mo). 135.5 weight partsof the impregnation solution was incorporated into 100 weight parts ofalumina carrier to provide a metal-incorporated support material.

The impregnated carrier or metal-incorporated support material was thendried at 125° C. (257° F.) for a period of several hours to give a driedintermediate having an LOI of 7.9 wt % and a water pore volume of 0.331cc/g.

Aliquot portions of the dried intermediate were then each impregnatedwith a selection of one of the following four additives or additivemixtures to fill 92% of the pore volume of the dried intermediate: 100%dimethylformamide (DMF); 100% Arosurf MG-98 ether amines, which is amixture of the two ether amines of 3-(octyloxy) propylamine and3-(decyloxy) propylamine, wherein Arosurf MG-98 ether amines is aproduct marketed by Evonik Industries; a mixture of 40 vol %n-formylmorpholine (NFM) and 60 vol % Arosurf MG-98 ether amines; and amixture of 50 vol % DMF and 50 vol % NFM.

Certain of the physical properties of the individual organic additivesare presented in the following Table 2.

TABLE 2 Properties of Various Organics Ether amine Ether amine3-(Octyloxy) 3-(Decyloxy) DMF NFM propylamine propylamine Flash Point (°F.) 136 235 210 242 Molecular Weight 79.09 115.13 187.32 215.38 (g/mole)Boiling Point (° F.) 307.4 458.6 514.4 577.6 Melting Point (° F.) −77.873.4 N/A N/A Formula C₃H₇NO C₅H₉NO₂ C₁₁H₂₅NO C₁₃H₂₉NO Density (g/cc)0.944 1.145 0.85 0.85

EXAMPLE II

This Example II describes the general procedure used to test thecatalytic performance of the additive impregnated compositions describedin Example I, and it presents the performance results from their use inthe hydrodesulfurization and hydrodenitrogenation of a typical vacuumgas oil.

Each of the additive impregnated compositions of Example I was testedusing reactors of a high throughput catalyst testing unit under theconditions presented in the following Table 3.

TABLE 3 Reactor Test Conditions and Targets Hydrogen/Oil Ratio 4060scf/bbl Pressure 1350 psig LHSV 1 hr⁻¹ Temperature 698° F. TargetNitrogen 500 ppm HDN Reaction Order 0.86 HDN Apparent Activation Energy26 kcal/mole Target S 200 ppm HDS Reaction Order 1.3  HDS ApparentActivation Energy 33 kcal/mole

The feedstock used in the testing was a typical vacuum gas oil havingthe physical properties as presented in the following Table 4.

TABLE 4 Test Feedstock Properties Hydrogen (wt %) 11.65 Carbon (wt %)85.60 Nitrogen (wt %) 0.44 Sulfur (wt %) 2.05 Nickel (ppm) 1 Vanadium(ppm) 2.5 Basic Nitrogen (ppm) 1447 API Gravity 19.29 UV Aromatics 1 4.92 4.2 3 5.0 4+ 3.8 Total 18.0 MCR (wt %) 0.2 HTSD 50% (° F.) 774 HTSD95% (° F.) 980

The results of the activity testing of the additive impregnatedcompositions are presented in the following Table 5. The catalystactivity, in this case, is defined as the temperature required toachieve a target concentration of nitrogen (500 ppm) or sulfur (200 ppm)in the treated product using a designated catalyst relative to thetemperature required to achieve the same concentration of nitrogen orsulfur in the treated product using a reference catalyst. With thisdefinition, larger negative activity numbers indicate higher activity.

TABLE 5 Catalyst Performance Results Relative HDN Relative HDSDescription Activity (° F.) Activity (° F.) 1 100% Arosurf MG-98 −10 −72 50/50 DMF/NFM −14 −10 3 40/60 NFM/Arosurf MG-98 −13 −10 4 100% DMF −5−2

The performance data presented in Table 5 show that the compositionwhich contains only ether amine as its additive exhibits very goodhydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activityrelative to the reference catalyst. This catalyst has particularly goodHDN activity, and, when compared to the catalyst having as its additiveonly the polar additive, DMF, it exhibits significantly better HDN andHDS activity. When the additive used is a mixture that combines theether amine with either DMF or NFM, in both cases, the HDN and HDSactivities are significantly improved over the activities exhibited bythe composition that contains the ether amine alone. These data suggesta synergistic effect resulting from using a combined mixture of theether amine with another additive.

1. A composition, comprising: a support material that is loaded with anactive metal precursor and an additive comprising at least 20 vol. % ofan ether amine compound.
 2. A composition as recited in claim 1, whereinsaid ether amine compound has a flash point of at least 80° C.
 3. Acomposition as recited in claim 2, wherein said ether amine compound hasa molecular weight greater than
 160. 4. A composition as recited inclaim 3, wherein said ether amine compound is miscible withn-formylmorpholine at a temperature of 25° C.
 5. A composition asrecited in claim 4, wherein said additive further comprisesn-formylmorpholine.
 6. A composition as recited in claim 5, wherein theweight ratio of n-formylmorpholine to said ether amine compound is inthe range of upwardly to 10:1.
 7. A composition as recited in claim 6,wherein said active metal precursor is a metal compound that includes aGroup 9 and Group 10 metal component selected from the group consistingof cobalt and nickel, and wherein said Group 9 and Group 10 metalcomponent is present in said composition in an amount in the range offrom 5 wt. % to 50 wt. %.
 8. A composition as recited in claim 7,wherein said support material that is loaded with said active metalprecursor and said additive is treated with hydrogen.
 9. A compositionas recited in claim 8, wherein said support material that is loaded withsaid active metal precursor and said additive and treated with hydrogenis treated with a sulfur compound.
 10. A method of making a composition,wherein said method comprises: incorporating a metal-containing solutioninto a support material to provide a metal-incorporated supportmaterial; and incorporating an additive comprising at least 20 vol. % ofan ether amine compound into said metal-incorporated support material tothereby provide an additive impregnated composition comprising at least20 vol. % of an ether amine compound.
 11. A method as recited in claim10, further comprising: contacting said additive impregnated compositionunder suitable hydrogen treatment conditions with hydrogen to therebyprovide a hydrogen-treated composition.
 12. A method as recited in claim11, wherein prior to said incorporating of said additive into saidmetal-incorporated support material, said metal-incorporated supportmaterial is dried so as to contain a volatiles content in the range offrom 3 to 20 wt. % LOI.